CN109364980A - A kind of preparation method and application preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium - Google Patents
A kind of preparation method and application preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium Download PDFInfo
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Abstract
The invention discloses a kind of preparation method and applications that mesoporous catalyst is prepared by chemical vapour deposition technique carried metal titanium.The present invention with it is cheap, with 3 D pore canal and TUD-1 that aperture is easy to regulate and control is carrier, carry out vapor deposition reaction with titanium-containing compound, then catalyst is made through silanization treatment.It is used for the epoxidation reaction of catalyzed alkene and alkyl peroxide, the problems such as existing epoxidation catalyst preparation cost is high, activity is low, and mass transfer effect is poor is solved, obtains good reaction effect.
Description
Technical field
The present invention relates to it is a kind of by chemical vapour deposition technique prepare mesoporous catalyst preparation method and its alkene with
Alkyl peroxide epoxidation produces the application in epoxides.
Background technique
Epoxides is extremely important and widely used organic chemical industry's intermediate, be often used to synthetic epoxy resin,
Surfactant, coating, binder and surface covering etc., demand is huge.The industrial technology of production epoxides is main at present
There are chlorohydrination, hydrogen peroxide direct oxidation method, conjugated oxidation (Halcon method).Chlorohydrination technical maturity, process be simple, raw material at
This low, small investment, but it is just gradually eliminated to the seriously polluted of the corrosion of equipment and environment.Hydrogen peroxide direct oxidation method
Process flow is simple, substantially pollution-free, but there are raw material, catalyst is expensive, H2O2The disadvantages of transport difficult.Cooxidation
Method is using alkyl peroxide as oxygen source, and the method that epoxidation of olefins produces epoxides pollutes small, reacting balance, yield
Height is the emphasis studied at present, has vast potential for future development.
In olefin epoxidation process its catalyst prepare it is particularly critical, many years study derived from it is homogeneous, heterogeneous out
Two major classes type catalyst.Homogeneous catalyst includes oxide, nitride, oxychloride, the fluorine of transition metal-type Ti, V, Mo, W etc.
Compound and its acylate, enolate, chelate, carbonyl compound etc., preparation process is simple, can be well soluble in reactant
In system, excellent catalytic effect, catalyst amount is few.But since catalyst is difficult to recycle in subsequent separation process, not only to product
Purity will cause influence, but also deposition can be decomposed in catalytic reaction process, and the fouling in reactor influences the property of reactor
Energy.In contrast, heterogeneous catalysis is easily isolated and recycled, stable structure, be recycled performance it is good, be saved greatly production
Cost, thus more advantage.
It is well known that titaniferous porous oxidation silicon materials are one of non-homogeneous catalysts, to the selection oxygen of olefines
Changing has good catalytic activity, can be used as the catalyst that alkene selective oxidation prepares epoxides.
So far, people are most studied and titanium silicalite material more thoroughly is TS-1.United States Patent (USP) US4410501 is first
Secondary to disclose the synthetic method of TS-1, elder generation contains using organosilicon acid esters, organic titanate, tetrapropylammonium hydroxide as raw material preparation
Then the colloidal silica solution of titanium is made through 6 ~ 30 days hydrothermal crystallizings again.The catalyst not only prepare it is harsher, crystallization time compared with
It is long, and aperture is smaller (d=0.55nm), it is impossible to be used in the higher macromolecular alkene (such as styrene) of catalysis carbon number or/and with
Alkyl peroxide is the epoxidation reaction of oxygen source, using being restricted, therefore needs the material of large aperture to solve the problems, such as this.
Since inventing the serial mesoporous material such as Ti-MCM-41 for the first time to Mobil company in 1992, then occur successively
A series of mesoporous material, such as Ti-SBA-15, Ti-HMS, these mesoporous materials are in macromolecular alkene or/and with alkyl peroxy
Change and is made great progress in the epoxidation reaction research that hydrogen is oxygen source.Current above-mentioned catalyst frequently with hydrothermal synthesis method or
The preparation of the methods of infusion process.Chinese patent CN1500004A and CN1248579A with hydrothermal synthesis method prepare Ti-MCM-41, and with
Hexamethyldisilazane is by its silanization, average pore size 2.8nm, in the reaction of ethylbenzene hydroperoxide (EBHP) cooxidation propylene
In have a preferable activity, but it uses expensive quaternary ammonium salt as template, and preparation cost is high, and hydrothermal stability is poor.
Compared with Ti-MCM-41, Ti-SBA-15 possesses thicker inorganic hole wall, thus possesses better hydrothermal stability.Using tradition
Hydrothermal synthesis method to prepare the finely dispersed Ti-SBA-15 of titanium more difficult, main cause is that its synthesis process is in acyclic acidic
The mismatch of the hydrolysis rate of border, titanium source and silicon source causes titanium to be difficult to enter the active site for forming high degree of dispersion in skeleton, causes
Keep catalyst activity relatively low.The prior art be during solving preparation Ti-SBA-15 titanium source and silicon source hydrolysis rate mismatch and
The problem for causing activity relatively low has done many work." chemical journal " 2 phases of volume 61 in 2003: 202-207 passes through first by metatitanic acid fourth
The presoma that ester and acetylacetone,2,4-pentanedione effect generate titanium reduces the hydrolysis rate of titanium, thus reach in acid condition with silicon source water
Solution matches, and the Ti-SBA-15 titanium of preparation is scattered.Chinese patent CN1235799C with soluble fluoride (NaF or
NH4F it is) catalyst, improves the hydrolysis rate of silicon source, thus reach the hydrolysis rate to match in acid condition with titanium source,
Its catalyst Ti prepared is efficiently entering in framework of molecular sieve.It can be seen that in order to match the hydrolysis rate of titanium source and silicon source,
The adjusting of the preparation condition carried out to prepare the catalyst that dispersion degree is high, catalytic activity is good can all be such that synthesis process becomes
It is more complicated and harsh.Compared with hydrothermal synthesis method, catalyst prepared by infusion process easily forms large-sized TiO outside skeleton2,
Titanium, which is more difficult to enter, forms active site in skeleton, cause catalytic activity relatively low.Chinese patent CN1234699C is with TiCl4Dipping
Ti/MCM-41 is prepared on MCM-41, is used for ethylbenzene hydroperoxide (EBHP) cooxidation by catalyst made from silanization treatment
In the reaction of 1- octene, the conversion ratio of EBHP is 77%, and catalyst activity is lower.
In conclusion more titanium-silicon molecular sieve TS-1 is studied at present because its aperture is smaller, it is higher for being catalyzed carbon number
Macromolecular alkene or/and lower as the Epoxidation activity of oxygen source using alkyl peroxide, using being restricted；Ti-MCM-
41, the mesoporous catalysts such as Ti-SBA-15 can be used for being catalyzed the higher macromolecular alkene of carbon number or/and using alkyl peroxide as oxygen
The epoxidation reaction in source, but when it uses hydrothermal synthesis method to prepare, has the characteristics that synthesis process is complicated, template used dose of valuableness,
Have the characteristics that the low caused poor catalytic activity of active site load capacity in skeleton when preparing using infusion process, limits industry and answer
With.
Based on this, seek a kind of preparation cost is cheap, preparation process is relatively easy, good hydrothermal stability, to alkene and alkane
The epoxidation reaction of base hydrogen peroxide has the preparation method of the mesoporous catalyst of greater activity to have very real meaning.
TUD-1 is a kind of novel mesoporous catalyst, synthesis process very simple, using three ethyl alcohol of non-surface-active agent
For amine as template, preparation cost is cheap, it has high-specific surface area, high hydro-thermal and high mechanical stability and hole parameter is easily adjusted
Advantage, especially three-dimensional communication duct can significantly reduce pore diffusion resistance, and reactant is made to be easier to enter duct participation instead
It answers, product, which is easier to be detached from, diffuses out duct, therefore often uses in the catalysis reaction for having diffusion to limit.Ti-TUD-1 is often closed with hydro-thermal
Prepare at method, such as " Journal of Catalysis " 260 phases in 2008: 288-294 use HMDS silanization hydrothermal synthesis method
The Ti-TUD-1 of preparation, in the reaction of tert-butyl hydroperoxide (TBHP) epoxidation 1- octene, activity is preferable, but it is being synthesized
In the process, there are the titanium source of use (butyl titanates) and silicon source (ethyl orthosilicate) hydrolysis rate to mismatch, and results in
The active poor or preferable activity of Ti-TUD-1 is not easy the problems such as reappearing.
Summary of the invention
In order to solve the problems such as existing epoxidation catalyst preparation cost is high, activity is low, and mass transfer effect is poor, the present invention is provided
It is a kind of the preparation method of mesoporous catalyst to be prepared by chemical vapour deposition technique and its in alkene and alkyl peroxide epoxidation
Produce the application in epoxides, use synthesis it is simple, it is cheap, with the TUD-1 that 3 D pore canal and aperture are easily adjusted be carrier and
Titanium-containing compound carries out chemical vapour deposition reaction, then catalyst is made through silanization treatment, and gained catalyst is in alkene and alkane
Good reaction effect is obtained in base hydrogen dioxide epoxidation reaction.Preparation method of the invention is by the adjustable carrier in aperture
Three steps such as preparation, vapor deposition, liquid phase silanization of TUD-1 are constituted, and three's interdependence is indispensable, and collaboration plays
Effect, and step is relatively easy, preparation cost is cheap, and the catalyst aperture of preparation is easily adjusted, and can pass through the adjusting pair in aperture
The epoxidation reaction of olefin hydrocarbon molecules and alkyl peroxide with different dynamic diameter has higher activity.
The purpose of the present invention is what is realized in the following way:
A kind of preparation method preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium, by following three step structure
At:
(1) by silicon source ethyl orthosilicate (TEOS), template triethanolamine (TEA), tetraethyl ammonium hydroxide (TEAOH) and water
(H2O mixing) is stirred at room temperature, the homogeneous phase solution of formation obtains carrier TUD-1 through aging, drying, heat treatment and calcining；
(2) it is fitted into tube furnace after carrier TUD-1 being milled, is pre-processed under nitrogen atmosphere, then contain with gasification
Titanium compound carries out vapor deposition reaction, uses N after reaction2The purging complete titanium-containing compound of removing unreacted until room temperature,
Ti/TUD-1 is made through roasting after taking-up；
(3) it disperses Ti/TUD-1 in organic solvent, organic silicon solution is then added, filter, wash after silanization treatment
It washs, be dried in vacuo, be made catalyst Ti/TUD-1 (S).
Further, in step (1), TEOS, TEA, TEAOH and H2The ratio between amount of substance of O is 1:(0.1 ~ 4): (0 ~
2): (1 ~ 35), preferably 1:(0.1 ~ 2): (0 ~ 1): (1 ~ 20), wherein do not include endpoint 0；Aging temperature is 20 ~ 60 DEG C, the time
For 12 ~ 72h；Drying temperature is 60 ~ 150 DEG C, and the time is 12 ~ 48h；When heat treatment the partial size of gel be 1 ~ 3000 μm, preferably 10 ~
1000 μm, heat treatment temperature be 60 ~ 280 DEG C, preferably 100 ~ 200 DEG C, the time be 0 ~ for 24 hours, preferably 0 ~ 12h；Calcination temperature is 500
~ 800 DEG C, the time is 5 ~ 15h.
Further, in step (2), the particle size range after carrier is milled is 0.1 ~ 1000 μm, preferably 1 ~ 800 μm；It is described
Vapor deposition reaction, reaction temperature be 500 ~ 900 DEG C, the reaction time be 0.5 ~ 3h；The maturing temperature is 500 ~ 800
DEG C, the time is 4 ~ 8h.
Further, in step (2), the titanium-containing compound of gasification is through N2Entrainment enters.
Further, in step (3), the organic solvent is benzene,toluene,xylene, isopropylbenzene, normal butane, isobutyl
One or more of alkane, pentane, n-hexane, hexamethylene, heptane, preferably benzene, toluene, isopropylbenzene and hexamethylene；It is described
Organic silicon solution be hexamethyldisilazane, hexamethyl chlorine silazane, seven methyl chloride silazane, trim,ethylchlorosilane, diformazan
Base chlorosilane, tetramethyl-disilazane, dimethyl diethoxysilane, trimethylmethoxysilane, dimethylformamide dimethyl oxygroup silicon
One or more of alkane, trimethylethoxysilane, silylamine and N- trimethyl-silyl-imidazole, preferably three
One or more of methylchlorosilane, hexamethyldisilazane, silylamine and N- trimethyl-silyl-imidazole,
Organosilicon dosage is the 0.1 ~ 100% of catalyst weight, and preferred scope is 30 ~ 70%；The reaction temperature of silanization treatment be 90 ~
180 DEG C, the reaction time is 2 ~ 10h.
Above-mentioned mesoporous catalyst is applied to alkene and the epoxidation reaction of alkyl peroxide in organic solvent, anti-
Answering temperature is 70 ~ 120 DEG C, and the time is 0.5 ~ 5h, and reaction pressure is 0.1 ~ 4MPa, and mass fraction of the catalyst in reaction solution is
0.5 ~ 5%, the mass fraction of alkyl peroxide in a solvent is 5 ~ 40%, and the mass ratio of the material of alkene and alkyl peroxide is
(0.5 ~ 20): 1.
Further, the alkene is C3-C10Olefine or cycloolefin；The alkyl peroxide is isopropylbenzene
Hydrogen peroxide, cyclohexyl hydroperoxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide；The solvent is isopropylbenzene, hexamethylene
Alkane, the tert-butyl alcohol, 1,2- dichloroethanes, ethylbenzene.
The beneficial effects of the present invention are:
Preparation method of the invention is walked by preparation, vapor deposition, liquid phase silanization of the adjustable carrier TUD-1 in aperture etc. three
Rapid to constitute, for three as an organic whole, interdependence is indispensable.
(1) present invention uses TUD-1 for carrier, and not only preparation cost is cheap, synthesis process is simple, gained 3 D pore canal
With large aperture, three-dimensional macropore can significantly reduce titanium-containing compound molecule in carrier in subsequent vapor deposition processes
The diffusional resistance of hole is deposited on more titaniums on carrier TUD-1, and catalytic activity is significantly improved.It is prepared by the present invention
Carry the advantage that titanium mesoporous catalyst possesses adjustable large aperture and three-dimensional open-framework compared with conventional mesoporous titanium-silicon material: adjustable
Large aperture the olefin hydrocarbon molecules of different dynamic diameter and alkyl peroxide can be made to contact in duct with titanium active site, from
And catalyst is made to possess higher activity；Three-dimensional cellular structure can significantly reduce reactant or the diffusion resistance of product molecule hole
Power makes olefin hydrocarbon molecules and alkyl peroxide be easier to enter duct participation reaction, and epoxy product, which is easier to be detached from, diffuses out duct,
Enhance mass transfer effect.
(2) present invention is deposited titanium-containing compound to TUD-1 using vapour deposition process, the catalyst activity position of preparation
Point height dispersion, catalytic activity is good, prepares simple and reproducible, effectively hydrothermal synthesis method can be avoided to prepare in catalyst process
Titanium source and silicon source hydrolysis rate mismatch and lead to problems such as active relatively low and active high catalyst synthesis processes complicated；Phase
Than being deposited under anaerobic in infusion process, it is not easy to be formed the large scale TiO outside skeleton2, active site high degree of dispersion urges
It is good to change activity.
(3) present invention carries out silylating reagent to the titanium silicalite material of preparation, and large aperture is more advantageous to three-dimensional open-framework
The diffusion and grafting of organosilicon, can not only improve the hydrophobic performance of catalyst surface, make alkene, alkyl peroxide molecule
It is easier to close with absorption, to react, promotes catalyst reaction activity；And the faintly acid on its surface can also be neutralized, it reduces secondary
The generation of reaction improves catalyst epoxidation selectivity.In addition, the change of roasting condition can significantly affect silane in deposition process
The hydrophilic and hydrophobic on the surface Ti/TUD-1 possesses different hydrophilic and hydrophobics under the conditions of identical silanization treatment before changing, thus
Possess different catalytic activity.
In short, three steps of the invention are all linked with one another, collaboration plays a role, and final gained catalyst is in alkene and alkyl
Extraordinary reaction effect can be obtained in the epoxidation reaction of hydrogen peroxide, and preparation step is relatively easy, preparation cost is low
It is honest and clean.
Specific embodiment
The present invention is further described below by way of specific embodiment, it should be noted that the following examples
It is used only as example, the contents of the present invention are not limited thereto.
Embodiment 1
Carrier TUD-1 preparation process: 25.06g triethanolamine (TEA) and 11.03g deionized water (H2O) after mixing, by it
Mixture is added drop-wise to dropwise in 35.00g ethyl orthosilicate (TEOS), and after stirring 0.5h, instilling 29.69g mass fraction is 25%
Tetraethyl ammonium hydroxide (TEAOH) aqueous solution, stirring 2h forming material amount ratio be 1TEOS:1TEA:0.3TEAOH:
11H2The homogeneous phase solution of O；Place is protected from light aging 2 days in room temperature；100 DEG C forced air drying 1 day in air dry oven；It gently mills sieving
Afterwards, control partial size is 900 ~ 2000 μm, and then 180 DEG C of rotations are heat-treated 4h in homogeneous reactor, finally with 5 in Muffle furnace
DEG C/600 DEG C of roasting 10h of heating rate of min, carrier TUD-1 is made.
Vapor deposition processes: 4.5gTUD-1 obtained above is placed in tube furnace, in 200ml/minN2400 under flow velocity
DEG C pretreatment 2h after, be rapidly heated to 700 DEG C, in 100ml/minN2150 DEG C of saturation TiCl are passed through under flow velocity4Steam 1.5h,
200ml/minN2Purging takes out after being cooled to room temperature under flow velocity, finally with 600 DEG C of the heating rate of 10 DEG C/min in Muffle furnace
6h is roasted, Ti/TUD-1 is obtained.
Silanization process: the above-mentioned Ti/TUD-1 of 3.0g is dispersed in 50.0g toluene, and 0.5 times of catalyst matter is then added
The HMDS of amount into suspension, under nitrogen atmosphere, 140 DEG C return stirring 5 hours.The powder filter that will be obtained, 50ml toluene
Washing three times, then dries 12h in vacuum oven at 110 DEG C, be made Ti/TUD-1 (S).Its titaniferous amount is 1.16%, is put down
Equal aperture is 7.8nm, Kong Rongwei 0.76cm3/g。
Embodiment 2
By catalyst prepared by above-described embodiment 1, in propylene and tert-butyl hydroperoxide epoxidation reaction, reaction
It is carried out in formula of having a rest reaction kettle.Rotor, 0.30g catalyst, 3.46g tert-butyl hydroperoxide and molten are successively added into reaction kettle
It seals after agent 27.44g1,2- dichloroethanes, then 16.2g propylene is added in kettle in liquid form by constant-flux pump.Through hunting leak
After place it in oil bath pan and react, in 120 DEG C of reaction 1h under pressure itself, take it to be put in ice water after reaction cooling
To 5 DEG C hereinafter, releasing unreacted propylene by exhaust valve and carrying out tail gas absorption with corresponding solvent.When determining in reaction kettle
Reaction solution is removed after noresidue gas and carries out qualitative and quantitative analysis.
Using the content of tert-butyl hydroperoxide in iodimetric analysis reaction solution, is analyzed and reacted using gas chromatogram fixative
The content of the propylene oxide of generation, internal standard compound are pentane.The conversion ratio of tert-butyl hydroperoxide is 97.4%, propylene oxide
Selectivity is 94.8%.
Embodiment 3
By the operating process of embodiment 1, it is with the difference of embodiment 1, when preparing carrier TUD-1, by mixing after aging
Liquid is put in 130 DEG C of forced air drying 12h in air dry oven, and the gel after drying is gently milled after sieving, and control partial size is 450
~ 900 μm, then 4h is heat-treated through 180 DEG C of rotations；Calcined carrier TUD-1 gently mills sieving, and control partial size is 150 ~ 200 μ
M, then carry out vapor deposition processes and Ti/TUD-1 (S) is made with silanization process.Its titaniferous amount is 1.20%, and average pore size is
18.1nm, Kong Rongwei 1.21cm3/g。
Embodiment 4
By the operating process of embodiment 3, it is with the difference of embodiment 3, when preparing carrier TUD-1, the amount of the substance of each raw material
Than pressing 1TEOS:1TEA:0.5TEAOH:20H2O is added, then is heat-treated 8h through 180 DEG C of rotations.Catalyst Ti/ obtained
TUD-1 (S) titaniferous amount is 1.39%, average pore size 32.9nm, Kong Rongwei 1.89cm3。
Ti/TUD-1 (S) is measured into its hydrophobic coefficient by following experimental procedure: (1) calculating the water absorption rate of catalyst: is accurate
Weighing 0.1000g catalyst and being placed in quality is m1Weighing bottle in, the weighing bottle for filling catalyst is then placed in vacuum drying
In 110 DEG C of vacuum drying 2h in case, weighing, quality m are taken out after cooling2, calculating dewatered catalyst quality is M=m2-
m1；Weighing bottle after weighing is placed in bottom to fill in the drier of 500ml distilled water, covering top cover, to be placed in 35 DEG C of constant temperature dry
48h is kept in dry case, take out and is precisely weighed, quality m3, the quality for calculating catalyst water suction is m=m3-m2；It is catalyzed
Water absorption rate=m/M of agent.(2) it calculates the oil absorbency of catalyst: pressing the operating procedure of (1), be with (1) difference, after weighing
Weighing bottle is placed in bottom and fills in the drier of 500ml normal octane (oil).(3) it calculates the hydrophobic coefficient of catalyst: repeating step (1)
(2) five times, taking water absorption rate average value is x, the average value of oil absorbency is y, calculates the hydrophobic coefficient=y/x of catalyst.By above-mentioned experiment
The hydrophobic coefficient that Ti/TUD-1 (S) is calculated is 64.83.
Embodiment 5
By the operating process of embodiment 4, it is with the difference of embodiment 4, by the maturing temperature in vapor deposition processes by 600 DEG C
700 DEG C are changed to, the hydrophobic coefficient of Ti/TUD-1 (S) obtained is 68.26.
Embodiment 6
By catalyst (being respectively labeled as 1#, 3#, 4# and 5#) prepared by above-described embodiment 1,3,4 and 5, for 1- amylene with it is different
In cumene hydroperoxide epoxidation reaction, reaction carries out in batch reactor.Catalysis is added first in inner liner of reaction kettle
Then the cumene oxidation liquid 5.14g that isopropyl benzene hydroperoxide mass percent is 25% is added, finally in agent 0.21g into liner
5.29g 1- amylene is added, inflated with nitrogen is to 1.5MPa after sealing kettle, in 100 DEG C of reaction 2h.After reaction, it is taken to be put in ice water
5 DEG C are cooled to hereinafter, opening the outlet valve of reaction kettle, the gas of releasing empties after isopropylbenzene absorbs.It extracts reaction solution and tail gas
The mixing of absorbing liquid isopropylbenzene, detection to be analyzed.
Reaction front and back isopropyl benzene hydroperoxide content is analyzed using iodometric titrationiodimetry titration, is analyzed using gas chromatogram fixative anti-
The content for 1, the 2- epoxypentane that should be generated, internal standard compound are isooctane.Reaction evaluating result see the table below:
1 different catalysts reaction evaluating result of table
| Catalyst | CHP conversion ratio % | 1,2- epoxypentane selectivity % |
| 1# | 84.6 | 88.7 |
| 3# | 84.8 | 94.2 |
| 4# | 90.4 | 89.3 |
| 5# | 91.5 | 90.1 |
Comparative example 1
It takes the commercially available MCM-41 carrier of 4.5g to prepare catalyst according to the vapor deposition processes and silanization process of embodiment 1 to be denoted as
Ti/ MCM-41 (S), average pore diameter 3.1nm.By the operating process of embodiment 2, exist with the difference of embodiment 2
In selected catalyst is Ti/ MCM-41 (S).The conversion ratio of tert-butyl hydroperoxide is 84.0%, the selection of propylene oxide
Property is 80.3%.
Comparative example 2
The commercially available SBA-15 carrier of 4.5g is taken to prepare catalyst note according to the vapor deposition processes and silanization process of embodiment 1
For Ti/SBA-15 (S), average pore diameter 5.6nm.By the operating process of embodiment 2, exist with the difference of embodiment 2
In selected catalyst is Ti/SBA-15 (S).The conversion ratio of tert-butyl hydroperoxide is 97.1%, the selectivity of propylene oxide
It is 90.1%.
Comparative example 3
Take the commercially available SiO of 4.5g2Carrier is prepared catalyst according to the vapor deposition processes and silanization process of embodiment 1 and is denoted as
Ti/SiO2(S), average pore diameter 9.7nm.By the operating process of embodiment 2, with embodiment 2 the difference is that, institute
The catalyst of choosing is Ti/SiO2(S).The conversion ratio of tert-butyl hydroperoxide is 95.2%, and the selectivity of propylene oxide is 89.6%.
Comparative example 4
It is added without catalyst, 1- amylene is carried out and is reacted with isopropyl benzene hydroperoxide epoxidation reaction blank.I.e. successively to reaction kettle
The cumene oxidation liquid 5.14g that isopropyl benzene hydroperoxide mass percent is 25% is added in liner, is eventually adding 5.29g 1- penta
Alkene, inflated with nitrogen is to 1.5MPa after sealing kettle, in 100 DEG C of reaction 2h.After reaction, take its be put in ice water be cooled to 5 DEG C hereinafter,
The outlet valve of reaction kettle is opened, the gas of releasing empties after isopropylbenzene absorbs.It extracts reaction solution mixed with tail gas absorption liquid isopropylbenzene
After conjunction, analysis detection.The conversion ratio of isopropyl benzene hydroperoxide is 8.8%, and the selectivity of 1,2- epoxypentane is 15.9%.
Comparative example 5
Hydrothermal synthesis method prepares Ti-TUD-1 (S).35.00g ethyl orthosilicate (TEOS) is added dropwise to dropwise under stirring
In tetraethyl ammonium hydroxide (TEAOH) aqueous solution of 29.69g 25wt.%, mixed liquor A is formed；By 1.14g butyl titanate
(TBOT) it is added dropwise to dropwise in the 25.06g triethanolamine (TEA) under stirring, forms mixed liquid B；Mixed liquid B is instilled dropwise again
In mixed liquor A under stirring, after stirring 1h, then 11.03g deionized water (H is added dropwise2O 0.5h, the ratio between amount of forming material) are stirred
For 1TEOS:0.02TBOT:0.3TEAOH:1TEA:11H2The homogeneous phase solution of O.It is protected from light place aging 48h in room temperature；Air blast
100 DEG C of forced air dryings are for 24 hours in drying box；180 DEG C of rotations are heat-treated 4h in homogeneous reactor after gently milling；Finally in Muffle
Template agent removing is removed with the heating rate of 5 DEG C/min, 600 DEG C of roasting 10h in furnace, Ti-TUD-1 is made.Most afterwards through phase in embodiment 1
Ti-TUD-1 (S) is made in same silanization process, and titaniferous amount is 1.14%.0.21g Ti-TUD-1 (S) is taken to carry out embodiment 5
Reaction evaluating, the conversion ratio of isopropyl benzene hydroperoxide is 73.7%, and the selectivity of 1,2- epoxypentane is 85.0%.
Comparative example 6
Infusion process prepares Ti ~ TUD-1 (S).Carrier TUD-1 preparation method and embodiment 1 are same, are then loaded on 4.5gTUD-1
In tube furnace, in 200ml/minN2After purging lower 550 DEG C of pretreatments 2h, N2Purging is cooled to room temperature and takes out for use；Measure 72ml
Dehydrated alcohol is added in 250ml three-necked flask, then inwardly sequentially adds 3.62g pretreated TUD-1,1.56gTiCl4, in
It is stirred to react 4h at 35 DEG C, is taken out after solvent evaporated, is put in Muffle furnace and is roasted with 850 DEG C of the heating rate of 10 DEG C/min
0.5h obtains Ti/TUD-1.Catalyst is made through the identical silanization treatment of embodiment 1 and is denoted as Ti ~ TUD-1 (S), titaniferous amount is
2.15%.0.21g Ti ~ TUD-1 (S) is taken to carry out the reaction evaluating of embodiment 5, the conversion ratio of isopropyl benzene hydroperoxide is 56.6%,
The selectivity of 1,2- epoxypentane is 72.9%.
Comparative example 7
The catalyst Ti/TUD-1 of non-silanization in embodiment 1 is added, carries out 1- amylene and isopropyl benzene hydroperoxide epoxidation is anti-
It answers.By the operating process of embodiment 5, the difference is that, selected catalyst is the Ti/ of non-silanization with embodiment 5
TUD-1.The conversion ratio of isopropyl benzene hydroperoxide is 53.9%, and the selectivity of 1,2- epoxypentane is 65.9%.
From the result of embodiment 2 and comparative example 1 ~ 3 can be seen that comparative example 1 ~ 3 be respectively adopted MCM-41, SBA-15,
SiO2For carrier, Ti/MCM-41 (S), Ti/SBA-15 (S), Ti/ is prepared by vapor deposition processes and silanization treatment
SiO2(S), compared with them, the Ti/TUD-1 (S) of same method preparation of the present invention, to the ring of propylene and tert-butyl hydroperoxide
Oxidation activity significantly improves.
It can be seen that from the result of embodiment 1 and comparative example 4,5,6 in the case where catalyst is not added, CHP does not turn substantially
Change, the selectivity of 1,2- epoxypentane is extremely low.And when being added, hydrothermal synthesis method prepares Ti-TUD-1 (S), infusion process prepares Ti/
When the catalyst such as the Ti/TUD-1 (S) that TUD-1 (S) and the present invention are prepared with vapour deposition process, 1- penta is improved significantly
The efficiency of the epoxidation reaction of alkene and CHP.The Ti/TUD-1 (S) that in the present invention prepared by vapour deposition process compares hydrothermal synthesis legal system
Standby Ti-TUD-1 (S) and Ti/TUD-1 prepared by infusion process (S), it is obvious more to 1- amylene and the activity of CHP epoxidation reaction
Height illustrates that the effect of catalyst obtained by the present invention is good.
From the result of embodiment 1 and comparative example 7 can be seen that the Ti/TUD-1 (S) by silanization treatment compared with without
When the Ti/TUD-1 of silanization treatment is used for 1- amylene epoxidation reaction, the selectivity of 1,2- epoxypentane promotes 20% or more, receives
Rate improves 35% or more, illustrates the carrier preparation and vapor deposition processing of silanization treatment collaboration front, obtains gained catalyst
Apparent effect promoting.
It can be seen that catalyst titaniferous amount obtained by the present invention from 1#, 3# and 4# of embodiment 6 to be promoted, be used for 1- penta
In alkene and isopropyl benzene hydroperoxide epoxidation reaction, the yield of isopropyl benzene hydroperoxide conversion ratio and 1,2- epoxypentane has
It is promoted, illustrates that the preparation of carrier cooperates with subsequent vapor deposition processing and silanization treatment, gained catalyst is made to obtain effect
It is promoted.
The change that can be seen that the roasting condition of vapor deposition processes from the 1# and 5# of embodiment 6 improves catalyst
Hydrophilic and hydrophobic causes isopropyl benzene hydroperoxide conversion ratio and 1, and the yield of 2- epoxypentane is promoted, and illustrates gas phase
The preparation of deposition processes synergistic carriers and silanization treatment make gained catalyst obtain effect promoting.
It can be seen that the preparation of the adjustable carrier TUD-1 in aperture, three vapor deposition, silanization processes are to prepare to have
The key of high epoxidation activity catalyst Ti/TUD-1 (S), three's interdependence is indispensable, and performance can be cooperateed with to make
With being not only embodied in the difference of carrier, be also embodied in the difference of processing method.
Claims (9)
1. a kind of preparation method for preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium, which is characterized in that by
It is constituted under following three step:
(1) it is by silicon source ethyl orthosilicate, that is, TEOS, template triethanolamine, that is, TEA, tetraethyl ammonium hydroxide, that is, TEAOH and water
H2Mixing is stirred at room temperature in O, and the homogeneous phase solution of formation obtains carrier TUD-1 through aging, drying, heat treatment and calcining；
(2) it is fitted into tube furnace after carrier TUD-1 being milled, is pre-processed under nitrogen atmosphere, then contain with gasification
Titanium compound carries out vapor deposition reaction, uses N after reaction2The purging complete titanium-containing compound of removing unreacted until room temperature,
Ti/TUD-1 is made through roasting after taking-up；
(3) it disperses Ti/TUD-1 in organic solvent, organic silicon solution is then added, be filtered, washed after silanization treatment,
Vacuum drying is made catalyst Ti/TUD-1 (S).
2. the preparation side according to claim 1 for preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium
Method, which is characterized in that in step (1), TEOS, TEA, TEAOH and H2The ratio between amount of substance of O is 1:(0.1 ~ 4): (0 ~ 2): (1
~ 35), wherein do not include endpoint 0.
3. the preparation side according to claim 1 for preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium
Method, which is characterized in that in step (1), aging temperature is 20 ~ 60 DEG C, and the time is 12 ~ 72h；Drying temperature is 60 ~ 150 DEG C, when
Between be 12 ~ 48h；The partial size of gel is 1 ~ 3000 μm when heat treatment, and heat treatment temperature is 60 ~ 280 DEG C, and the time is 0 ~ 12h, and not
Including endpoint 0, calcination temperature is 500 ~ 800 DEG C, and the time is 5 ~ 15h.
4. the preparation side according to claim 1 for preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium
Method, which is characterized in that in step (2), the particle size range after carrier is milled is 0.1 ~ 1000 μm；The vapor deposition reaction,
Reaction temperature is 500 ~ 900 DEG C, and the reaction time is 0.5 ~ 3h；The titanium-containing compound of gasification is through N2Entrainment enters；Maturing temperature is
500 ~ 800 DEG C, the time is 4 ~ 8h.
5. the preparation side according to claim 1 for preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium
Method, which is characterized in that in step (3), the organic silicon solution is hexamethyldisilazane, hexamethyl chlorine silazane, seven first
Base chlorine silazane, trim,ethylchlorosilane, dimethylchlorosilane, tetramethyl-disilazane, dimethyl diethoxysilane, trimethyl
Methoxy silane, dimethyldimethoxysil,ne, trimethylethoxysilane, silylamine and N- trimethyl silyl miaow
One or more of azoles, organosilicon dosage are the 0.1 ~ 100% of catalyst weight；The reaction temperature of silanization treatment is
90 ~ 180 DEG C, the reaction time is 2 ~ 10h.
6. the preparation side according to claim 1 for preparing mesoporous catalyst by chemical vapour deposition technique carried metal titanium
Method, which is characterized in that in step (3), the organic solvent be benzene,toluene,xylene, isopropylbenzene, normal butane, iso-butane,
One or more of pentane, n-hexane, hexamethylene, heptane, preferably benzene, toluene, isopropylbenzene and hexamethylene.
7. the mesoporous catalyst of preparation method preparation as claimed in any one of claims 1 to 6 is applied to alkene and alkyl peroxy
The epoxidation reaction of hydrogen in organic solvent.
8. application according to claim 7, which is characterized in that reaction temperature is 70 ~ 120 DEG C, and the time is 0.5 ~ 5h, reaction
Pressure is 0.1 ~ 4Mpa, and mass fraction of the catalyst in reaction solution is 0.5% ~ 5%, the quality of alkyl peroxide in a solvent
Score is 5% ~ 40%, and the mass ratio of the material of alkene and alkyl peroxide is (0.5 ~ 20): 1.
9. application according to claim 7, which is characterized in that the alkene is C3-C10Olefine or cycloolefin；Institute
The alkyl peroxide stated is isopropyl benzene hydroperoxide, cyclohexyl hydroperoxide, tert-butyl hydroperoxide, ethylbenzene hydroperoxide；
The solvent is isopropylbenzene, hexamethylene, the tert-butyl alcohol, 1,2- dichloroethanes, ethylbenzene.
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